Cationic group 3 catalyst system

ABSTRACT

A cationic Group 3 or Lanthanide metal complex for coordination polymerization of olefins is disclosed. The precursor metal complex is stabilized by a monoanionic bidentate ancillary ligand and two monoanionic ligands. The ancillary ligand and the transition metal form a metallocycle having at least five primary atoms, counting any π-bound cyclopentadienyl group in the metallocycle as two primary atoms. Olefin polymerization is exemplified.

RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No.09/408,050, filed on Sep. 29, 1999 now U.S. Pat. No. 6,403,773.Application Ser. No. 09/408,050 claims priority from U.S. ProvisionalApplication Ser. No. 60/102,420, filed Sep. 30, 1998.

FIELD OF THE INVENTION

This invention relates to certain transition metal compounds from Group3 of the Periodic Table of Elements, and to a catalyst system comprisinga Group 3 or Lanthanide transition metal compound and alumoxane,modified alumoxane, non-coordinating anion activator, Lewis acid, or thelike to form an active cationic catalyst species for the production ofpolyolefins such as polyethylene, polypropylene and alpha-olefincopolymers of ethylene and propylene having a high molecular weight.

BACKGROUND OF THE INVENTION

Neutral scandium compounds having two univalent ancillary ligands or abidentate, divalent ancillary ligand are known from Shapiro et al.,Organometallics, vol. 9, pp. 867-869 (1990); Piers et al., J. Am. ChemSoc., vol. 112, pp. 9406-9407 (1990); Shapiro et al., J. Am. Chem Soc.,vol. 116, pp. 4623-4640 (1994); Hajela et al., Organometallics, vol. 13,pp. 1147-1154 (1994); and U.S. Pat. No. 5,563,219 to Yasuda et al.Similar yttrium, lanthanum and cerium complexes are disclosed in Booijet al., Journal of Organometallic Chemistry, vol. 364, pp. 79-86 (1989)and Coughlin et al., J. Am. Chem. Soc., vol. 114, pp. 7606-7607 (1992).Similar polymerizations with a metal scandium complex having abidentate, divalent ancillary ligand using a non-ionizing cocatalyst isknown from U.S. Pat. No. 5,464,906 to Patton et al.

Group 3-10 metallocyclic catalyst complexes are described in U.S. Pat.Nos. 5,312,881 and 5,455,317, both to Marks et al.; U.S. Pat. No.5,064,802 to Stevens et al.; and EP 0 765 888 A2.

Polymerization of olefins with cationic Group 4 metal complexes isillustrated in WO 96/13529 and WO 97/42228. Boratabenzene complexes ofGroup 3-5 metals are disclosed in WO 97/23493.

Amidinato complexes of Group 3-6 metals are disclosed in U.S. Pat. No.5,707,913 to Schlund et al. Group 4 bisamido catalysts are disclosed inU.S. Pat. No. 5,318,935 to Canich, et al., and related bidentatebisarylamido catalysts are disclosed by D. H. McConville, et al,Macromolecules 1996, 29, 5241-5243.

SUMMARY OF THE INVENTION

The present invention is directed to a catalyst system for coordinationpolymerization comprising a cationic Group 3 or Lanthanide metalstabilized by a monoanionic bidentate ancillary ligand and twomonoanionic ligands. The ancillary ligand, together with the metal,forms a metallocycle comprising a ring of at least five primary atoms,counting any η⁵-bonded cyclopentadienyl in the metallocycle as twoprimary metallocycle atoms. The metal is preferably scandium, yttrium orlanthanum.

In one embodiment, the monoanionic bidentate ancillary ligand, A, hasthe formula (C₅H_(4-x)R_(x))TE wherein x is a number from 0 to 4denoting the degree of substitution; each R is, independently, a radicalselected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or any other radicalcontaining a Lewis acidic or basic functionality, C₁-C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements, andhalogen radicals, or C₅H_(4-x)R_(x) is a cyclopentadienyl ring in whichtwo adjacent R-groups are joined to form a C₄-C₂₀ ring to give asaturated or unsaturated polycyclic cyclopentadienyl ligand which mayadditionally be substituted with R groups, and may contain a heteroatomwithin the ring; T is a covalent bridging group containing a Group 14 or15 element; and E is a π donating hydrocarbyl, π donatingheterohydrocarbyl, or other π-donating ligand covalently bound to T suchas, for example, allyl, phenyl, benzyl, pyridyl or the like, or E isJR′_(z) wherein J is an element from Group 15 or 16, z is 2 when J is aGroup 15 element and 1 when J is a Group 16 element, each R′ isindependently a radical selected from C₁-C₂₀ hydrocarbyl radicals,substituted C₁-C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen atom, and C₁-C₂₀ hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements.

Heterocyclic pi donating ligands wherein one to three ring carbons ofthe C₅H_(4-x)R_(x) ligand is replaced by a Group 15 or 16 heteroatom;substituted or unsubstituted boratabenzene ligands; substituted orunsubstituted allyl ligands; substituted or unsubstituted pentadienylligands; or other delocalized pi-bonded ligands may also be used inplace of the C₅H_(4-x)R_(x)ligand.

In another embodiment, as represented by structure (I), the monoanionicbidentate ancillary ligand, A, has the formula —NR′=T′—NR′-wherein N isnitrogen and T′ is a covalent bridging group selected from═C(R)-[C(R)═C(R)]_(η)- and

wherein each R′ is independently as defined above, each R isindependently as defined above, except that R independently may also behydrogen except for R groups attached to the carbon atoms directlybonded to the nitrogen atoms.

In a further embodiment, a typical polymerization process according tothe present invention, such as the polymerization or copolymerization ofolefins, comprises the steps of activating the transition metalcomponent to a cationic form and contacting ethylene or C₃-C₂₀alpha-olefins alone or with other unsaturated monomers including C₃-C₂₀alpha-olefins, C₅-C₂₀ diolefins, and/or acetylenically unsaturatedmonomers, either alone or in combination with other olefins and/or otherunsaturated monomers, with a catalyst comprising, in a suitablepolymerization diluent, the activated cationic transition metalcomponent of the invention. The catalyst is activated with an alumoxane,modified alumoxane, non-coordinating anion activator, Lewis acid or thelike, or combinations, in an amount to provide a molar ratio ofaluminum, non-coordinating anion, or Lewis acid to transition metal offrom about 1:10 to about 20,000:1 or more; and reacts with themonomer(s) at a temperature from about −100° C. to about 300° C. for atime from about one second to about 10 hours to produce a polyolefinhaving a weight average molecular weight of from about 1000 or less toabout 5,000,000 or more and a molecular weight distribution of fromabout 1.5 to about 15.0 or greater.

DETAILED DESCRIPTION OF THE INVENTION

The Group 3 transition metal component of the catalyst system of theinvention can be defined broadly by the formula:

wherein M is a Group 3 or Lanthanide metal;

A is a monoanionic, bidentate ancillary ligand which forms ametallocycle with M comprising at least 5 primary atoms, provided thatany cyclopentadienyl group or other delocalized pi-bonded ligand in themetallocycle is counted as two primary metallocycle atoms; each Q isindependently a monoanionic ligand such as a radical selected fromhalide, hydride, substituted or unsubstituted C₁-C₂₀ hydrocarbyl,hydrocarbylsilyl, alkoxide, aryloxide, amide or phosphide or both Qtogether may be an alkylidene or a cyclometallated hydrocarbyl or anyother divalent anionic chelating ligand, or a diene, with the provisothat where any Q is a hydrocarbyl radical, such Q is not a substitutedor unsubstituted cyclopentadienyl radical;

L is a neutral Lewis base such as, for example, diethyl ether,tetrahydrofuran, dimethylaniline, trimethylphosphine, lithium chlorideor the like, and can also be optionally covalently bound to one or bothQ, provided Q is not hydride or halide. L can also be a secondtransition metal of the same type, i.e. the transition metal componentcan be dimeric; and

w is a number from 0 to 3.

In cationic form as activated for olefin polymerization, the transitionmetal complex has the formula:

wherein M, A, Q, L and w are as defined above and A′ is a weakly ornoncoordinating anion which counterbalances the cationic complex.

In a preferred embodiment, the transition metal component of thecatalyst system has the formula:

wherein C₅H_(4-x)R_(x) is typically a cyclopentadienyl ring covalentlyπ-bound to M and substituted with from zero to four substituent groupsR, x is a number from 0 to 4 denoting the degree of substitution, andeach R is, independently, a radical selected from C₁-C₂₀ hydrocarbylradicals, C₁-C₂₀ substituted hydrocarbyl radicals wherein one or morehydrogen atoms are replaced by a halogen atom, amido, phosphido, alkoxyor aryloxy or any other radical containing a Lewis acidic or basicfunctionality, C₁-C₂₀ hydrocarbyl-substituted metalloid radicals whereinthe metalloid is selected from Group 14 of the Periodic Table of theElements, and halogen radicals, or C₅H_(4-x)R_(x) is a cyclopentadienylring in which two adjacent R-groups are joined to form a C₄-C₂₀ ring togive a saturated or unsaturated polycyclic cyclopentadienyl ligand whichmay additionally be substituted with R groups, and may contain aheteroatom within the ring; C₅H_(4-x)R_(x) may alternatively be replacedwith a heteroatom-containing 5-membered monovalent anionic ring groupcovalently π-bound to M, said heteroatoms being selected from thenon-carbon Group 13-15 atoms, preferably boron, silicon, germanium,nitrogen or phosphorus. Most typically one heteroatom will replace oneof the carbon atoms in the 5-member ring. Additionally, two or moreadjacent R groups may be joined to form a 4 to 20 atom ring forming asaturated or unsaturated polycyclic cyclopentadienyl ligand which mayadditionally contain a non-carbon group 14-16 heteroatom within thering. Such ligands are described in WO 98/22486 which is referred to forinformation and incorporated by reference for purposes of U.S. patentpractice.

T is a covalent bridging group containing a Group 14 or 15 element suchas, but not limited to, a dialkyl, alkylaryl or diaryl silicon orgermanium radical, alkyl or aryl phosphine or amine radical, or ahydrocarbyl radical such as methylene, ethylene, isopropylene or thelike.

J is a Group 15 or 16 element; z is 2 when J is a Group 15 element and 1when J is a Group 16 element; each R is independently a radical selectedfrom C₁-C₂₀ hydrocarbyl radicals and substituted C₁-C₂₀ hydrocarbylradicals wherein one or more hydrogen atoms is replaced by a halogenatom, amido, phosphido, alkoxy, aryloxy, metalloid or any other radicalcontaining a Lewis acidic or basic functionality, and C₁-C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements.

Q, L and w are defined above.

Exemplary hydrocarbyl radicals for Q in all of the above formulae aremethyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl,octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl, benzyl and the like,with benzyl being preferred. Exemplary halogen atoms for Q includechlorine, bromine, fluorine and iodine, with chlorine being preferred.Exemplary alkoxides and aryloxides for Q are methoxide, phenoxide andsubstituted phenoxides such as 4-methyl-phenoxide. Exemplary amides forQ are dimethylamide, diethylamide, methylethylamide, di-t-butylamide,diisopropylamide and the like. Exemplary arylamides are diphenylamideand any other substituted phenylamides. Exemplary phosphides for Q arediphenylphosphide, dicyclohexylphosphide, diethylphosphide,dimethylphosphide and the like. Exemplary alkylidene radicals for both Qtogether are methylidene, ethylidene and propylidene. Exemplarycyclometallated hydrocarbyl radicals for both Q together are propylene,and isomers of butylene, pentylene, hexylene and octylene. Exemplarydienes for both Q together are 1,3-butadiene, 1,3-pentadiene,1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene,2,4-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,2-methyl-1,3-hexadiene and 2,4-hexadiene.

Suitable hydrocarbyl radicals, for R or R′ in all the above formulae,will contain from 1 to about 20 carbon atoms and include straight andbranched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substitutedcyclic hydrocarbon radicals, aromatic radicals, alkyl-substitutedaromatic radicals. Suitable substituted hydrocarbyl radicals arehydrocarbyl radicals as defined above which are independentlysubstituted with one or more halogen, amido, phosphido, alkoxy,metalloid or other Lewis acidic or basic functionality, such as,trifluoromethyl, dimethylaminomethyl, diphenylphosphinomethyl,methoxymethyl, phenoxyethyl trimethylsilylmethyl and the like. Suitableorganometallic radicals for R or R′, in all the above formulae includetrimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl,triphenylgermyl and the like.

In cationic form activated for olefin polymerization, themonocyclopentadienyl transition metal complex has the formula:

wherein M, C₅H_(4-x)R_(x)R, x, T, J, z, R′, L, w and A′ are as definedabove.

In an alternative embodiment, the transition metal component of thecatalyst system has one of the formulae:

wherein n is 1, 2, 3 or 4 and M, N, Q, L, w, R′ and R are as definedabove, except that R independently may also be hydrogen except for the Rgroups attached to the carbon atoms directly bonded to the nitrogenatoms.

In cationic forms activated for olefin polymerization the transitionmetal complexes of formulae (VI) and (VII) have the representativeformulae:

wherein M, N, R, R′, Q, L, w, n and A′ are as defined above.

Table 1 below depicts representative constituent moieties for the Group3 or Lanthanide transition metal components of the present catalystsystem, but the list is for illustrative purposes only and should not beconstrued to be limiting in any way. A number of final compounds may beformed by permuting possible combinations of the constituent moietieswith each other. Some changes in nomenclature may be required. Forexample, if 1,2-dimethylcyclopentadienyl is bridged via the “5”position, it can become 2,3-dimethylcyclopentadienyl. When a specificisomer is not specified, all possible isomers are included. For example,when Q=propoxy, n-propoxy, and i-propoxy are included. Specificrepresentative examples includecyclopentadienyl-dimethylsilylene-pyridyl-scandium-dihydride;methylcyclopentadienyl-phenylene-dimethylamino-yttrium-dichloride;tetramethylcyclopentadienyl-methylphenylsilylene-diphenylamino-lanthanum-diethyl;and the like.

TABLE 1 M Q C₅H_(4−x)R_(x) T JR’_(z) —NR′═T′—NR′— candium HydrideCyclopentadienyl Methylene (z = 1) N,N′-bis(2,6-dimethylphenyl)-3-imino-1,3-dimethylpropeneanimato ttrium Chloro Methylcyclopentadienyl Ethylenemethoxy N,N′-bis(2,6-trimethylphenyl)-3-imino- 1,3-dimethylpropeneanimato anthanum Fluoro Ethylcyclopentadienyl Propylene ethoxyN,N′-bis(2,6-diethylphenyl)-3-imino-1, 3-dimethyl propeneanimato eriumBromo n-propylcyclopentadienyl Butylene propoxyN,N′-bis(2,6-diisopropyl-phenyl)-3-imi- no-1,3-dimethyl propeneanimatoraseo- Iodo i-propylcyclopentadienyl 1,2-cyclohexylene pentoxyN,N′-bis(2-methylphenyl)-3-imino-1,3- dymiu dimethylpropeneanimatoeodymium Methyl n-butylcyclopentadienyl 1,2-cyclooctylene hexoxyN-(2-methylphenyl)-N′-(2-ethylphenyl)- 3-imino-1,3-dimethylpropeneanimato amarium Ethyl t-butylcyclopentadienyl 1,2-cyclododecyleneheptoxy uropium n-propyl (cyclohexylmethyl) o-phenylene octoxyN-(2-methylphenyl)-N′-(2-ethylphenyl)- cyclopentadienyl3-imino-1,3-dimethyl propeneanimato adolinium isopropyln-hexylcyclopentadienyl m-phenylene phenoxy erbium n-butyln-octylcyclopentadienyl o-xylylene benzyloxyN-(2-methylphenyl)-N′-(2-isopropyl- phenyl)-3-imino-1,3-dimethylpropenea- nimato ysprosium isobutyl β- m-xylylene methylthiophenylpropylcyclopentadienyl olmium amyl PhenylcyclopentadienylDimethylsilylene ethylthio N,N′-bis(2,6-dimethylphenyl)-3-imino-1,3-dimethylpropeneanimato rbium isoamyl BenzylcyclopentadienylDiethylsilylene propylthio hulium hexyl (diphenylmethyl)di-n-propylsilylene methylseleneno N-phenyl-7-(phenylimino)-1,3,5-cyclo-cyclopentadienyl heptatrien-1-ylanimato tterbium heptyl Trimethylgermyl-Diisopropylsilylene phenylseleneno cyclopentadienyl utetium octylTrimethylstannyl- di-n-butylsilylene (z = 2)N-(2,6-dimethylphenyl)-7-(2,6- cyclopentadienyldimethylphenylimino)-1,3,5-cyclohepta- trien-1-ylanimato nonylTriethylplumyl- di-n-hexylsilylene dimethylamino cyclopentadienyl M QC₅H_(4−x)R_(x) T E L decyl Trifluoromethyl- Methylphenylsilylenediethylamino N-phenyl-7-(2,6-dimethylphenyl)- cyclopentadienyl1,3,5-cycloheptatrien-1-ylanimato cetyl Trimethylsilyl- Diphenylsilylenedipropylamino cyclopentadienyl phenyl 1,2-dimethylcyclopentadienylDicyclohexylsilylene dibutylamino N-phenyl-7-(phenylimino)-2,4,5-trimethyl-1,3,5-cycloheptatrien-1- ylanimato benzyl1,3-dimethylcyclopentadienyl Tetramethyldisilylene dipentylamino(trimethylsilyl) 1,2-diethylcyclopentadienyl Tetraphenyldisilylenedicyclopentylamino methyl methoxy 1,3-diethylcyclopentadienylTetramethyldisiloxene dihexylamino ethoxy 1,3-di-n-Pentamethyldisilazene dicyclohexylamino propylcyclopentadienyl propoxy1,3-diphenylcyclopentadienyl bis(1,1-methylene) methylcyclo-dimethylsilane hexylamino butoxy 1,2-diphenylcyclopentadienyl1,1-bis(dime- methylphenylamino thylsitylene)methane phenoxy 1-methyl-3-1,1,4,4-tetra- methyl-n- phenylcyclopentadienyl methyldisilylethylenehexylamino dimethylamido 1-methyl-3-t- Methylazanediyl methylphenyl-butylcyclopentadienyl phosphino diethylamido 1-methyl-3- Ethylazanediyldimethylphosphino isopropylcyclopentadienyl methylethylamido1-methyl-3-n- i-butylazanediyl diphenylphosphino butylcyclopentadienyldi-t-butylamido 1-cyclohexyl-3- t-butylazanediyl dicyclohexyl-methylcyclopentadienyl phosphino diphenylamido Indenyl n-hexylazanediyldimethylarsenio diphenylphosphido 2-methylindenyl n-octylazanediyldiphenylarsenio dicyclohexyl- 2-methyl-4-phenylindenyl Phenylazanediylphosphido Dimethylphosphido 2-methyl-4-napthylindenyl p-n- allyl diethylether butylphenylazanediyl Methylidene 4-phenylindenyl 2,5-di-t- phenylTetrahydrofuran butylphenylazanediyl Ethylidene 2-isopropylindenylPerfluoro- benzyl Dimethylaniline phenylazanediyl Propylidene2-isopropyl-4-phenylindenyl Benzylazanediyl napthyl Trimethylphosphine1,3-butadiene 2,3-dimethylindenyl Cyclohexylazanediyl pyridyl lithiumchloride 2,4-dimethyl-1,3- 2,3,4,6-tetramethylindenylCyclooctylazanediyl pyrrolyl Ethylene butadiene 1,3-pentadiene2-methylbenzindenyl Cyclodecylazanediyl 2H-pyrrolyl 1-butene1,4-pentadiene Tetrahydroindenyl Cyclododecylazanediyl imidazolyl2-butene 1,3-hexadiene 4,7-dimethylindenyl 2-norbornylazanediylpyrazolyl Trimethylamine 1,4-hexadiene 2,4,7-trimethylindenyl1-adamantylazanediyl isothiazolyl tri-n-butylamine 1,5-hexadieneFluorenyl Ethylphosphinediyl isoxazolyl tri-n-butylamine 2,4-hexadiene2,7-di-t-butylfluorenyl Phenylphosphinediyl pyrazinyl styrene2-methyl-1, 2,7-dimethylfluorenyl Cyclohexyl- furyl p-methylstyrene3-hexadiene phosphinediyl 2-methyl-1, Octahydrofluorenyl pyranylpropylene 3-pentadiene 2-methyl-7-t-butylfluorenyl tetrahydrofuryloctene Silacyclopentadienyl thienyl Germacyclopentadienyl pyrimidylAzacyclopentadienyl pyridazinyl Phosphacyclopentadienyl pyrrolinylAzaindenyl imidazolinyl 2,6-dimethylazapentalene pyrazolinyloctahydrooctamethylfluorenyl silabenzene boratabenzene allyl pentadienyl3,3-dimethylcyclohexadienyl

Metal complexes according to the invention can be prepared by variousconventional synthetic routes.

The metal compounds according to the invention are suitable forcoordination polymerization when activated by methods known in themetallocene art. Suitable activators typically include alumoxanecompounds, modified alumoxane compounds, and ionizing anion precursorcompounds that abstract one reactive, sigma bound metal ligand therebyionizing the metal center into a cationic complex and providing acounter-balancing weakly or noncoordinating anion, which can optionallybe bound to the cationic complex so as to form a Zwitterionic catalyst.

Alkylalumoxanes and modified alkylalumoxanes are suitable ascatalyst-activators, particularly for the invention metal compoundscomprising halide ligands. The alumoxane component useful as a catalystactivator typically is an oligomeric aluminum compound represented bythe general formula (R²—Al—O)_(m), which is a cyclic compound, orR³(R⁴—Al—O)_(m)AlR₂, which is a linear compound, although otherstructural variations may exist. In the general alumoxane formula eachR²-R⁵ is independently a C₁ to C₂₀ hydrocarbyl radical, for example,methyl, ethyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl, and m is aninteger from 1 to about 50. Most preferably, R²-R⁵ is methyl and m is atleast 4. If an alkyl aluminum halide is used in the alumoxanepreparation, the R²-R⁵ can also be halide. Alumoxanes can be prepared byvarious procedures known in the art. For example, an aluminum alkyl maybe treated with water dissolved in an inert organic solvent, or it maybe contacted with a hydrated salt, such as hydrated copper sulfatesuspended in an inert organic solvent, to yield an alumoxane. Generally,however prepared, the reaction of an aluminum alkyl with a limitedamount of water yields a mixture of the linear and cyclic species of thealumoxane. Methylalumoxane and modified methylalumoxanes are preferred.Mixtures of different alumoxanes and modified alumoxanes may also beused. For further descriptions, see U.S. Pat. Nos. 4,665,208, 4,952,540,5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018,4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516 476 A, EP 0 594218 A1 and WO 94/10180, each being incorporated by reference forpurposes of U.S. patent practice.

When the activator is an alumoxane, the preferred transition metalcompound to activator molar ratio is from about 1:5000 to 1:1, morepreferably from about 1:1000 to 1:10, even more preferably from about1:500 to 1:10 and most preferably from about 1:100 to 1:10.

The term “noncoordinating anion” is recognized to mean an anion,as-represented by the symbol A′ above, which either does not coordinateto the metal cation or which is only weakly coordinated to it therebyremaining sufficiently labile to be displaced by a neutral Lewis base,such as an olefinically or acetylenically unsaturated monomer.

Descriptions of ionic catalysts, those comprising a transition metalcationic complex and a noncoordinating anion, suitable for coordinationpolymerization appear in the early work in U.S. Pat. Nos. 5,064,802,5,132,380, 5,198,401, 5,278,119, 5,321,106, 5,347,024, 5,408,017,5,599,671, and WO 92/00333 and WO 93/14132. These teach a preferredmethod of preparation wherein metallocenes are protonated bynoncoordinating anion precursors such that an alkyl/hydride group isabstracted making the transition metal compound both cationic andcharge-balanced by the noncoordinating anion. Since similar ligands maybe present in the metal compounds of the invention, similar methods ofactivation to prepare active polymerization catalysts may be followed. Apreferred hydrocarbyl radical Q serving as an abstractable ligand isbenzyl.

Preferred noncoordinating anion precursors of this type include those offormula [R*₃GH][ZX*_(4-a)R*_(a)] where R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a Group 15 element, preferably nitrogen, H is aproton capable of reacting with the Group 3 or Lanthanide metal complex,Z is a group 13 element, preferably boron or aluminum, X* isindependently a substituted or unsubstituted fluorocarbyl orfluorohydrocarbyl ligand, preferably a substituted or unsubstitutedaromatic fluorocarbyl or fluorohydrocarbyl ligand, and a is 0, 1 or 2.Most preferred X* radicals include perfluorophenyl, perfluoronapthyl,perfluorobiphenyl, and 3,5-bis(trifluoromethyl)phenyl. The preferredcationic portion of the noncoordinating anion precursors include[Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH], [(C₁₆H₃₃)₃NH], [(C₁₈H₃₇)₃NH] andthe like. The preferred anionic portion of the noncoordinating anionprecursors include [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃) ₄], [B(C₆F₅)₃(C₁₀F₇)] and the like where C₆F₅ isperfluorophenyl, C₁₀F₇ is perfluoronapthyl and C₁₂F₉ isperfluorobiphenyl.

The use of ionizing ionic compounds not containing an active proton butcapable of producing both an active metal cationic complex and anoncoordinating anion is also possible. See, EP-A-0 426 637, EP-A-0 573403 and U.S. Pat. No. 5,387,568 for instructive ionic compounds.Reactive cations of the ionizing ionic compounds, other than theBronsted acids, include ferrocenium, silver, tropylium, carbeniumcations including triphenylcarbenium and silylium cations includingtriethylsilylium, or alkali metal or alkaline earth metal cations suchas sodium, magnesium or lithium cations. A further class ofnoncoordinating anion precursors suitable in accordance with thisinvention are hydrated salts comprising the alkali metal or alkalineearth metal cations and a non-coordinating anion as described above. Thehydrated salts can be prepared by reaction of the metalcation-noncoordinating anion salt with water, for example, by hydrolysisof the commercially available or readily synthesized [Li]⁺[B(pfp)₄]⁻which yields [Li(H₂O)_(x)]⁺[B(pfp)₄]⁻, where (pfp) is pentafluorophenylor perfluorophenyl.

Any metal or metalloid capable of forming a compatible, weakly ornegligibly coordinating complex may be used or contained in thenoncoordinating anion. Suitable metals include, but are not limited toaluminum, gold, platinum and the like. Suitable metalloids include, butare not limited to, boron, phosphorus, silicon and the like. Thedescription of noncoordinating anions and precursors thereto of thedocuments of the foregoing paragraphs are incorporated by reference forpurposes of U.S. patent practice.

An additional method of making the active polymerization catalysts ofthis invention uses ionizing anion precursors which are initiallyneutral Lewis acids but form a metal cationic complex and thenoncoordinating anion, or a Zwitterionic complex upon reaction with theinvention compounds. For example, tris(pentafluorophenyl) boron oraluminum act to abstract a hydrocarbyl or hydride ligand to yield aninvention metal cationic complex and stabilizing noncoordinating-anion,see EP-A-0 427 697 and EP-A-0 520 732 for illustration utilizinganalogous Group 4 metallocene compounds. See also the methods andcompounds of EP-A-0 495 375. For formation of Zwitterionic complexesusing analogous Group 4 compounds see U.S. Pat. Nos. 5,624,878;5,486,632; and 5,527,929. The description of noncoordinating anions andprecursors thereto of these documents are similarly incorporated byreference for purposes of U.S. Patent practice. Lewis acid activatorsinclude those of formula ZX*_(3-b)R*_(b) where Z, X* and R* are asdefined above and b is 0 or 1. Preferred Lewis acid activators includeB(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃, Al(C₁₂F₉)₃ andthe like.

When the cation portion of an ionic noncoordinating anion precursor is aBronsted acid such as protons or protonated Lewis bases (excludingwater), or a reducible Lewis acid such as ferrocenium or silver cations,or alkaline metal or alkaline earth metal cations such as those ofsodium, magnesium or lithium cations, or a neutral Lewis base such asB(C₆F₅)₃ or Al(C₆F₅)₃, the transition metal to activator molar ratio maybe any ratio, but preferably from about 10:1 to 1:10, more preferablyfrom about 5:1 to 1:5, even more preferably from about 2:1 to 1:2 andmost preferably from about 1.2:1 to 1:1.2 with the ratio of about 1:1being the most preferred. Combinations of the activator compoundsdescribed may also be used for activation. For example,tris(perfluorophenyl) boron can be used in conjunction withmethylalumoxane.

The catalyst complexes of the invention are useful in polymerization ofunsaturated monomers conventionally known to be polymerizable undercoordination polymerization conditions using metallocenes. Suchconditions are well known and include solution polymerization, slurrypolymerization, gas-phase polymerization, and high pressurepolymerization. The catalyst of the invention may be supported and assuch will be particularly useful in the known operating modes employingfixed-bed, moving-bed, fluid-bed, slurry or solution processes conductedin single, series or parallel reactors.

When using the catalysts of the invention, particularly when immobilizedon a support, the total catalyst system will generally additionallycomprise one or more scavenging compounds. The term “scavengingcompounds” as used in this application and its claims is meant toinclude those compounds effective for removing polar impurities from thereaction environment. Impurities can be inadvertently introduced withany of the polymerization reaction components, particularly withsolvent, monomer and catalyst feed, and adversely affect catalystactivity and stability. It can result in decreasing or even eliminationof catalytic activity, particularly when ionizing anion pre-cursorsactivate the catalyst system. The polar impurities, or catalyst poisonsinclude water, oxygen, metal impurities, etc. Preferably steps are takenbefore provision of such into the reaction vessel, for example bychemical treatment or careful separation techniques after or during thesynthesis or preparation of the various components, but some minoramounts of scavenging compound will still normally be used in thepolymerization process itself.

Typically the scavenging compound will be an organometallic compoundsuch as the Group 13 organometallic compounds of U.S. Pat. Nos.5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,and that of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, triisobutyl aluminum, methylalumoxane, isobutylaluminumoxane, and tri-n-octyl aluminum. Those scavenging compoundshaving bulky or C₆-C₂₀ linear hydrocarbyl substituents covalently boundto the metal or metalloid center are preferred to minimize adverseinteraction with the active catalyst. Examples include triethylaluminum,but more preferably, bulky compounds such as triisobutylaluminum,triisoprenylaluminum, and long-chain linear alkyl-substituted aluminumcompounds, such as tri-n-hexylaluminum, tri-n-octylaluminum, ortri-n-dodecylaluminum. When alumoxane is used as activator, any excessover the amount needed to activate the catalysts present will act asscavenger compounds and additional scavenging compounds may not benecessary. Alumoxanes also may be used in scavenging amounts with othermeans of activation, e.g., methylalumoxane, [Me₂HNPh]⁺[B(pfp)₄]⁻ orB(pfp)₃. The amount of scavenging agent to be used with the catalystcompounds of the invention is minimized during polymerization reactionsto that amount effective to enhance activity and avoided altogether ifthe feeds can be sufficiently free of adventitious impurities.

The catalyst according to the invention may be supported for use in gasphase, bulk, slurry polymerization processes, or otherwise as needed.Numerous methods of support are known in the art for copolymerizationprocesses for olefins, particularly for catalysts activated byalumoxanes, any are suitable for the invention process in its broadestscope. See, for example, U.S. Pat. Nos. 5,057,475 and 5,227,440. Anexample of supported ionic catalysts appears in WO 94/03056. Aparticularly effective method is that described U.S. Pat. No. 5,643,847,and WO 96/04319. A bulk, or slurry, process utilizing supported,invention metal compounds activated with alumoxane co-catalysts can beutilized as described for ethylene-propylene rubber in U.S. Pat. Nos.5,001,205 and 5,229,478, and these processes will additionally besuitable with the catalyst systems of this application. Both inorganicoxide and polymeric supports may be utilized in accordance with theknowledge in the field. See U.S. Pat. Nos. 5,422,325, 5,427,991,5,498,582 and 5,466,649, and international publications WO 93/11172 andWO 94/07928. Each of the foregoing documents is incorporated byreference for purposes of U.S. patent practice.

In preferred embodiments of the process for this invention, the catalystsystem is employed in liquid phase (solution, slurry, suspension, bulkphase or combinations thereof), in high pressure liquid or supercriticalfluid phase, or in gas phase. Each of these processes may be employed insingular, parallel or series reactors. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the copolymers in accordance with theinvention. Hydrocarbyl solvents are suitable, both aliphatic andaromatic, hexane and toluene are preferred. Bulk and slurry processesare typically done by contacting the catalysts with a slurry of liquidmonomer, the catalyst system being supported. Gas phase processestypically use a supported catalyst and are conducted in any manner knownto be suitable for ethylene homopolymers or copolymers prepared bycoordination polymerization. Illustrative examples may be found in U.S.Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,382,638, 5,352,749,5,436,304, 5,453,471, and 5,463,999, and WO 95/07942. Each isincorporated by reference for purposes of U.S. patent practice.

Generally speaking the polymerization reaction temperature can vary fromabout −50° C. to about 250° C. Preferably the reaction temperatureconditions will be from −20° C. to 220°, more preferably below 200° C.The pressure can vary from about 1 mm Hg to 2500 bar, preferably from0.1 bar to 1600 bar, most preferably from 1.0 to 500 bar.

Linear polyethylene, including high and ultra-high molecular weightpolyethylenes, including both homo- and copolymers with otheralpha-olefin monomers, alpha-olefinic and/or non-conjugated diolefins,for example, C₃-C₂₀ olefins, C₄-C₂₀ diolefins, C₄-C₂₀ cyclic olefins orC₈-C₂₀ styrenic olefins, are produced by adding ethylene, and optionallyone or more of the other monomers, to a reaction vessel at a typicaltemperature of 20-250° C. with the invention catalyst that has beenslurried with or dissolved in a solvent, such as hexane or toluene. Heatof polymerization is typically removed by cooling. Gas phasepolymerization can be conducted, for example, in a continuous fluid bedgas-phase reactor operated at about 200-3000 kPa and 60-160° C., usinghydrogen as a reaction modifier (100-200 ppm), C₄-C₈ comonomerfeedstream (0.5-12 mol %), and C₂ feedstream (25-35 mol %). See, U.S.Pat. Nos. 4,543,399, 4,588,790, 5,028,670 and 5,405,922 and 5,462,999,which are incorporated by reference for purposes of U.S. patentpractice.

Ethylene-α-olefin (including ethylene-cyclic olefin andethylene-α-olefin-diolefin) elastomers of high molecular weight and lowcrystallinity can be prepared utilizing the catalysts of the inventionunder traditional solution polymerization processes or by introducingethylene gas into a slurry utilizing the α-olefin or cyclic olefin ormixtures thereof with other monomers, polymerizable and not, as apolymerization diluent in which the invention catalyst is suspended.Typical ethylene pressures will be between 10 and 1000 psig (69-6895kPa) and the polymerization diluent temperature will typically bebetween −10-160° C. The process can be carried out in a stirred tankreactor, or more than one reactor operated in series or parallel. Seethe general disclosure of U.S. Pat. No. 5,001,205 which is incorporatedby reference for its description of polymerization processes, ionicactivators and useful scavenging compounds.

Pre-polymerization of the supported catalyst of the invention may alsobe used for further control of polymer particle morphology in typicalslurry or gas phase reaction processes in accordance with conventionalteachings. For example, such can be accomplished by pre-polymerizingethylene or a C₃-C₆ α-olefin for a limited time, for example, ethyleneis contacted with the supported catalyst at a temperature of −15° to 30°C. and ethylene pressure of up to about 250 psig (1724 kPa) for 75 minto obtain a polymeric coating on the support of polyethylene of30,000-150,000 molecular weight. The pre-polymerized catalyst is thenavailable for use in the polymerization processes referred to above. Theuse of polymeric resins as a support coating may additionally beutilized, typically by suspending a solid support in dissolved resin ofsuch material as polystyrene with subsequent separation and drying.

Other olefinically unsaturated monomers besides those specificallydescribed above may be polymerized using the catalysts according to theinvention, for example, styrene, alkyl-substituted styrene, ethylidenenorbornene, norbornadiene, dicyclopentadiene, vinylcyclohexane,vinylcyclohexene and other olefinically-unsaturated monomers, includingother cyclic olefins, such as cyclopentene, -norbornene, andalkyl-substituted norbornenes. Additionally, α-olefinic macromonomers ofup to 1000 mer units, or more, may also be incorporated bycopolymerization.

The catalyst compositions of the invention can be used as describedabove individually for coordination polymerization or can be mixed toprepare polymer blends with other known olefin polymerization catalystcompounds. By selection of monomers, blends of coordination catalystcompounds, polymer blends can be prepared under polymerizationconditions analogous to those using individual catalyst compositions.Polymers having increased MWD for improved processing and othertraditional benefits available from polymers made with mixed catalystsystems can thus be achieved.

EXAMPLES

The following examples are presented to illustrate the foregoingdiscussion. All parts, proportions, and percentages are by weight unlessotherwise indicated. All reactions and manipulations have been conductedusing dry, oxygen-free solvents under an inert nitrogen or argonatmosphere. Although the examples may be directed toward certainembodiments of the present invention, they are not to be viewed aslimiting the invention in any specific respect. In these examples,certain abbreviations are used to facilitate the description. Theseinclude standard chemical abbreviations for the elements and certaincommonly accepted abbreviations, such as: Me=methyl, Et=ethyl, Bu=butyl,Ph=phenyl, MAO=methylalumoxane, and THF=tetrahydrofuran.

All molecular weights are weight average molecular weight unlessotherwise noted. Molecular weights (weight average molecular weight (Mw)and number average molecular weight (Mn)) were measured by GelPermeation Chromatography, unless otherwise noted, using a Waters 150Gel Permeation Chromatograph equipped with a differential refractiveindex detector and calibrated using polystyrene standards. Samples wererun in either THF (45° C.) or in 1,2,4-trichlorobenzene (145° C.)depending upon the sample's solubility using three Shodex GPC AT-80 M/Scolumns in series. This general technique is discussed in “LiquidChromatography of Polymers and Related Materials III” J. Cazes Ed.,Marcel Decker, 1981, page 207, which is incorporated by reference forpurposes of U.S. patent practice herein. No corrections for columnspreading were employed; however, data on generally accepted standards,e.g. National Bureau of Standards Polyethylene 1475, demonstrated aprecision with 0.1 units for Mw/Mn which was calculated from elutiontimes. The numerical analyses were performed using Expert Ease® softwareavailable from Waters Corporation. The term “psid” refers to thedifferential pressure resulting from the addition of monomer.

Example 1

Synthesis of(dimethylaminoethyl)tetramethylcyclopentadienyl-scandiumdichloride,(CH₂)₂(C₅Me₄)(NMe₂)ScCl₂(1)

To a solution of Li metal (10.2 g, 1.47 mol) in Et₂O (300 ml)2-bromo-2-butene (100 g, 0.74 mol) was added over 2 hours under andargon flow at a rate sufficient to maintain a reflux. The reaction wasstirred for 4 hours at ambient temperature and thenethyl-3-(N,N-dimethylamino)propionate (50 g, 0.35 mole) was added over1.5 hours maintaining a reflux. The reaction was stirred for 15 hours atambient temperature. The reaction was poured into aqueous NH₄Cl (200 ml)and stirred until all of the Li was deactivated. The phases wereseparated and the aqueous phase was extracted with Et₂O (4×100 ml). Thecombined organics were dried over MgSO₄, filtered and the solvent wasremoved under reduced pressure yielding an orange oil (50 g, 67 mol %).

The oil in Et₂O was added to a solution of p-toluenesulfonic acid.H₂O(47 g, 0.23 mol) in Et₂O. The reaction was stirred for 3 hours. Thereaction was poured into aqueous Na₂CO₃. The phases were separated andthe aqueous phase was extracted with Et₂O (3×50 ml). The combinedorganics were dried over MgSO₄, filtered, and the solvent was removedunder reduced pressure yielding an orange oil. The oil was distilled atreduced pressure (35-40° C./0.010 torr) yielding a yellow oil (24.1 g,55 mol %).

In a drybox n-BuLi (10.3 ml, 0.026 mol) was added to a solution of thecompound prepared above (5.0 g, 0.026 mol) in pentane (150 ml) and thereaction stirred overnight. The solution was filtered, washed withpentane, and the solid dried.

The above solid (2.17 g, 0.011 mol) was dissolved in THF and ScCl₃ (1.65g, 0.011 mol) was added over several minutes. The reaction was stirredfor 18 hours, filtered, and the THF removed under reduced pressureyielding a red oil. Petroleum ether was added to the oil and theresulting solution filtered to yield an orange solid (3.1 g, 92 mol %).

Example 2

Synthesis of(dimethylaminoethyl)tetramethylcyclopentadienyl-scandiumdibenzyl,(CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ (2)

In a drybox (CH₂)₂(C₅Me₄)(NMe₂)ScCl₂ (1.33 g, 0.00431 mol) was slurriedin toluene. To this solution benzyl Grignard (2.0 M in THF, 6 ml) wasadded over 20 minutes. The reaction was stirred for 16 hours, filtered,and the solid washed with toluene. The solvent was removed under reducedpressure. Toluene was added to the solid, the solution was filtered andthe toluene removed under reduced pressure, and the resultingyellow-orange solid dried (1.6 g, 89 mol %). The solid wasrecrystallized from toluene to give pale yellow crystals. The structureof this compound was confirmed by a single crystal x-ray analysis.

Example 3

Formation of [(CH₂)₂(C₅Me₄)(NMe₂Sc(CH₂C₆H₅)]⁺[(C₆H₅CH₂)B-(C₆F₅)₃]⁻ andPolymerization of Ethylene (3)

In the drybox (CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ (12 mg, 0.0286 mmol) wasloaded into an NMR tube and dissolved in toluene-d₈. To this solution,B(C₆F₅)₃ (15 mg, 0.029 mmol) was added and the solution turned yellow.Within several minutes a yellow oil had separated out. Ethylene (10 ml,99.99+%) was added to the tube through a cap via a gas tight syringe.Within several minutes polymer was noticeable on the walls of the tube.

Example 4

Ethylene polymerization with (CH₂)₂(C₅Me₄)(NMe₂)ScCl₂ (4)

Polymerization runs were carried out in a 1 L reactor using the catalystsystem prepared by activation of (CH₂)₂(C₅Me₄)(NMe₂)ScCl₂ withmethylalumoxane. The catalyst was prepared with an aluminum to scandiummolar ratio of 925/1. The polymerizations were carried out in 400 ml oftoluene at 80° C. for 15 minutes under 65 psid (4.5 bars) continuousethylene pressure. The catalyst produced 2.8 g of polyethylene with anactivity of 781 kgPE/molSc•atm•h. The product obtained had Mw of 370,000and MWD of 2.11 indicative of single site catalyst behavior.

Example 5

Ethylene/Hexene Polymerization With (CH₂)₂(C₅Me₄)(NMe₂)ScCl₂ (5)

Polymerization runs were carried out in a 1 L reactor using the catalystsystem prepared by activation of (CH₂)₂(C₅Me₄)(NMe₂)ScCl₂ withmethylalumoxane. The catalyst was prepared with an aluminum to scandiummolar ratio of between 460-500/1. The polymerizations were carried outin 350 ml of toluene at 60° C. for 15 minutes with 50 ml of 1-hexene and65 psid (4.5 bars) continuous ethylene pressure. The catalyst produced1.0 g of ethylene-1-hexene copolymer with an activity of 93 kgpolymer/mol Sc•atm•h. The product obtained had an Mw of 441,000 and anMWD of 2.70 indicative of single site catalyst behavior. ¹H NMR of thepolymer indicated 3.5 mol % 1-hexene incorporated into the polymer.

Example 6

Ethylene Polymerization With (CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ andN,N-Dimethyanilinium Tetrakis-Perfluorophenyl Boron [DMAH]⁺[B(pfp)₄]⁻(6)

Polymerization runs were carried out using the catalyst system preparedby activation of (CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ with[DMAH]⁺[B(pfp)₄]⁻.(CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ (20 mg) was weighedout under inert atmosphere conditions and [DMAH]⁺[B(pfp)₄]⁻ activatorwas added in a 1/1 molar ratio. Dry toluene (2 ml) was added via pipetteand the mixture was allowed to stand (10-15 minutes) with occasionalstirring to allow for complete activation.

To a dry N₂-purged, 1 liter autoclave reactor dry toluene (0.4 L) wasadded. While the solvent was stirred under N₂-purge, triethylaluminum(25 wt % TEAL in heptane, 0.2 ml) was added as a scavenger to thereactor via syringe through a purge port using standard air sensitivetechnique. The reactor was then equilibrated to 80° C. The pre-activatedcatalyst was then added to the reactor through a port using airsensitive technique. The reactor was then pressurized with 65 psid (4.5bars) ethylene with a replenishing flow. The mixture was then stirred at80° C. for 15 minutes.

The polymer obtained was dried in a vacuum oven. The resulting polymer,1.3 g, had Mw=7000 and MWD=1.93 indicative of single site catalystbehavior. (catalyst activity=25 kg polymer/molSc•atm•h).

Example 7

Ethylene Polymerization With (CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ andN,N-Dimethyanilinium Tetrakis-Perfluorophenyl Boron,[DMAH]⁺[B(pfp)₄]⁻(7)

Polymerization runs were carried out using the catalyst system preparedby activation of (CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ with [DMAH]⁺[B(pfp)₄]⁻.(CH₂)₂(C₅Me₄)(NMe₂)Sc(CH₂C₆H₅)₂ (10 mg) was weighed out under inertatmosphere conditions and [DMAH]⁺[B(pfp)₄]⁻ activator was added with a1/1 molar ratio. Dry toluene (2 ml) was added via pipette and themixture was allowed to stand (10-15 minutes) with occasional stirring toallow for complete activation.

To a dry N₂-purged, 1 liter autoclave reactor dry toluene (0.4 L) wasadded. While the solvent was stirred under N₂-purge, triethylaluminum(25 wt % TEAL in heptane, 0.2 ml) was added as a scavenger to thereactor via syringe through a purge port using standard air sensitivetechnique. The reactor was then equilibrated to 80° C. The pre-activatedcatalyst was then added to the reactor through a port using airsensitive technique. The reactor was then pressurized with 65 psid (4.5bars) ethylene with a replenishing flow. The mixture was then stirred at80° C. for 15 minutes.

The polymer obtained was dried in a vacuum oven. The resulting polymer,0.9 g, had Mw=171,000 and bimodal MWD=10.96. (Catalyst activity=34 kgpolymer/mot Sc•atm•h).

Example 8

Synthesis ofN,N′-Bis-(2,6-diisopropylphenyl)-3-iminopropeneaminato-scandiumDichloride

The hydrochloride salt ofN,N′-bis-(2,6-diisopropylphenyl)-3-iminopropeneamine (0.487 g, 1.14mmol) was suspended into 15 ml of anhydrous THF at −80° C. n-Butyllithium (2.1 ml) was added dropwise to the stirred suspension. Uponcomplete addition, the solution was stirred and allowed to warm to roomtemperature over 50 minutes. The solution was then cooled to −80° C.whereupon 0.17 g (1.12 mmol) of anhydrous scandium trichloride wasadded. The reaction was stirred and allowed to warm to room temperatureover one hour. The THF was then removed in vacuo. The residue wasdissolved into hexane and filtered. The solution was dried in vacuo toremove solvent. The residue was dissolved into pentane forming twophases. The lighter pentane rich phase was separated and pentane removeduntil crystallization ensued. The crystalline solid was dried in vacuo.A ¹H-NMR was recorded in benzene. The spectrum clearly shows 1equivalent of coordinated THF. The chemical shifts are as follows: 11.6ppm, broad singlet (bs), 1H beta to NAr; 7.12 ppm, 6H, Ar-H; 4.80 ppm,t, 2H alpha to NAr; 3.60 ppm, m, 4H alpha to 0 in THF; 3.30 ppm, h, 4H,H-C(CH₃)₂; 1.35 ppm, m, 4H beta to O in THF; 1.19 ppm, d, 12H, CH ₃.

Example 9

Synthesis ofN,N′-Bis-(2,6-dimethylphenyl)-3-imino-1,3-dimethyl-propeneaminato-scandiumDichloride

The lithium salt ofN,N′-bis-(2,6-dimethylphenyl)-3-imino-1,3-dimethyl-propeneamine (1.02 g,3.3 mmol) was dissolved into 11 ml of anhydrous THF and cooled to −20°C. Separately, scandium trichloride (0.45 g, 3.0 mmol) was suspendedinto 11 ml of anhydrous THF and cooled to −20° C. The ligand solutionwas then added dropwise to the scandium suspension. Upon completeaddition, the mixture was stirred and slowly warmed to room temperature.The reaction was continued overnight. THF was then removed in vacuo. Theresidue was extracted with toluene and filtered. The solution wasconcentrated, hexane added and the solution cooled to −80° C. where theproduct crystallized as yellow microcrystals. The product was collectedby filtration and washed with pentane. The crystals were dried in vacuo.Isolated yield: 550 mg (44 mol %).

Example 10

Ethylene Polymerization WithN,N′-bis-(2,6-dimethylphenyl)-3-imino-1,3-dimethyl-propeneaminato-scandiumDichloride and MAO

To a 300 ml Parr reactor 203 milligrams of solid methylaluminoxane wasdissolved into 50 ml of toluene. Separately, 29 milligrams of thecompound from Example 9 was dissolved into approximately 1.5 ml oftoluene. This compound was activated by the addition of approximately1.5 ml of a toluene solution containing 203 milligrams of MAO. Theprepared catalyst had an aluminum to scandium molar ratio of 50:1. Thisactivated catalyst mixture was added to the reactor. The reactor wassealed and warmed to 40° C. The reactor was then charged with 40 psid(2.76 bars) of ethylene with a replenishing flow. Polymerization wascontinued for 30 minutes. The temperature was controlled to between 39and 45° C. The reactor was depressurized and 100 ml of 2 N aqueoushydrochloric acid was added. Polymer, 0.2 g, was collected by filteringthe resulting two phase solution. The catalyst had an activity of 1.6 kgPE/mol Sc•atm•hr. The polymer obtained had an M_(w) of 41,900 and an MWDof 3.6.

Example 11

Ethylene Polymerization with N,N′-bis-(2,6-dimethylphenyl)-3-imino-1,3-dimethyl-propeneaminato-scandium Dichloride and MAO

To a 300 ml Parr reactor 203 milligrams of solid methylaluminoxane wasdissolved into 50 ml of toluene. Separately, 29 milligrams of thecompound from Example 9 was dissolved into approximately 1.5 ml oftoluene. This compound was activated by the addition of approximately1.5 ml of a toluene solution containing 203 milligrams of MAO. Theprepared catalyst had an aluminum to scandium molar ratio of 50:1. Thisactivated catalyst mixture was added to the reactor. The reactor wassealed and warmed to 50° C. The reactor was then charged with 40 psid(2.76 bars) of ethylene with a replenishing flow. Polymerization wascontinued for 30 minutes. The temperature was controlled to between 47and 56° C. The reactor was depressurized and 100 ml of 2 N aqueoushydrochloric acid was added. Polymer, 0.16 g, was collected by filteringthe resulting two phase solution. The catalyst had an activity of 1.2 kgPE/mol Sc•atm•hr. The polymer obtained had an M_(w) of 42,100 and an MWDof 3.7.

Example 12

Comparative Example withN,N′-bis-(2,6-diisopropylphenyl)-3-iminopropeneaminat-scandiumDichloride and MAO

To a 300 ml Parr reactor 203 milligrams of solid methylaluminoxane wasdissolved into 50 ml of toluene. Separately, 40 milligrams of thecompound from Example 8 was dissolved into approximately 1.5 ml oftoluene. This compound was combined with MAO by the addition ofapproximately 1.5 ml of a toluene solution containing 203 milligrams ofthe MAO. The prepared catalyst had an aluminum to scandium molar ratioof 50:1. The reagent mixture/reaction product was colorless. It wasadded as such to the reactor. The reactor was sealed and warmed to 40°C. The reactor was then charged with 40 psid (2.76 bars) of ethylenewith a replenishing flow. The contacting of ethylene with the reagentmixture/reaction product was continued for 30 minutes. The temperaturewas controlled to between 37 and 43° C. The reactor was depressurizedand 100 ml of 2 N aqueous hydrochloric acid was added. No heat ofreaction nor polymer product was observed. This is believed to be due tothe use of hydrogen as R groups on the carbon atoms directly bonded tothe ketimato nitrogens of the metallocyclic ring. The strong Lewisacidity of the MAO likely deactivated the Scandium compound throughinadvertent byproduct reactions.

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

We claim:
 1. A catalyst system for coordination polymerizationcomprising: (1) an activator, and (2) a Group-3 or Lanthanide metalstabilize by a monoanionic bidentate ligand and two monoanionic ligands,wherein the bidentate ligand and the metal form a metallocyclic ringcomprising at least five primary atoms, where component (2) isrepresented by the formula:

wherein, M is a Group 3 or Lanthanide metal; A is a monoanionicbidentate ancillary ligand which forms a metallocycle with at least 5primary atoms, provided that any cyclopentadienyl group or otherdelocalized pi-bonded ligand in the metallocycle is counted as twoprimary metallocycle atoms; each Q is independently a monoanionicligand, with the proviso that where any Q is a hydrocarbyl radical, suchQ is not a substituted or unsubstituted cyclopentadienyl radical; L is aneutral Lewis base; and w is a number from 0 to
 3. 2. The catalystsystem of claim 1 wherein the metal comprises scandium or yttrium.
 3. Acatalyst system for coordination polymerization comprising: (1) anactivator, and (2) a Group-3 or Lanthanide metal stabilize by amonoanionic bidentate ligand and two monoanionic ligands, wherein thebidentate ligand and the metal form a metallocyclic ring comprising atleast five primary atoms, where component (2) is represented by theformula:

wherein, M is a Group 3 metal; A is a monoanionic bidentate ancillaryligand which forms a metallocycle with at least 5 primary atoms,provided that any cyclopentadienyl group or other delocalized pi-bondedligand in the metallocycle is counted as two primary metallocycle atoms;each Q is independently a monoanionic ligand, with the proviso thatwhere any Q is a hydrocarbyl radical, such Q is not a substituted orunsubstituted cyclopentadienyl radical; L is a neutral Lewis base; and wis a number from 0 to
 3. 4. A catalyst system for coordinationpolymerization comprising: (1) an activator, and (2) a Group-3 orLanthanide metal stabilize by a monoanionic bidentate ligand and twomonoanionic ligands, wherein the bidentate ligand and the metal form ametallocyclic ring comprising at least five primary atoms, wherecomponent (2) is represented by the formula:

wherein M is a group 3 or Lanthanide metal; C₅H_(4-x)R_(x) is acyclopentadienyl ring covalently π-bound to M and substituted with fromzero to four substituent groups R; x is a number from 0 to 4 denotingthe degree of substitution of C₅H_(4-x)R_(x); each R is, independently,a radical selected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or other Lewisacidic or basic group, C₁-C₂₀ hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, halogen radicals, or C₅H_(4-x)R_(x) is a cyclopentadienylring in which two adjacent R-groups are joined to form a C₄-C₂₀ ring togive a saturated or unsaturated polycyclic cyclopentadienyl ligand whichis optionally substituted with one or more R groups; T is a covalentbridging group containing a Group 14 or 15 element; L_(w) is a neutralLewis base; w is a number from 0 to 3; J is a Group 15 or 16 element; zis 2 when J is a Group 15 element and 1 when J is a Group 16 element;each R′ is independently a radical selected from C₁-C₂₀ hydrocarbylradicals, substituted C₁-C₂₀ hydrocarbyl radicals wherein one or morehydrogen atoms is replaced by a halogen atom, and C₁-C₂₀hydrocarbyl-substituted metalloid radical wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements; and each Qis independently a univalent anionic ligand, with the proviso that whereany Q is a hydrocarbyl radical, such Q is not a substituted orunsubstituted cyclopentadienyl radical.
 5. A catalyst system forcoordination polymerization comprising: (1) an activator, and (2) aGroup-3 or Lanthanide metal stabilize by a monoanionic bidentate ligandand two monoanionic ligands, wherein the bidentate ligand and the metalform a metallocyclic ring comprising at least five primary atoms, wherecomponent (2) is represented by one of the formulae:

wherein M is a Group 3 or Lanthanide metal; each R is independentlyhydrogen, halogen, a C₁-C₂₀ hydrocarbyl, or a substituted C₁-C₂₀hydrocarbyl wherein one or more hydrogen atoms is replaced by a halogenatom, amido, phosphido, alkoxy or aryloxy or other Lewis acidic or basicgroup, C₁-C₂₀ hydrocarbyl-substituted metalloid radical wherein themetalloid is selected from Group 14 of the Periodic Table of theElements, or two adjacent R-groups are joined to form a C₄-C₂₀ ring,except that each R is optionally hydrogen except for R groups attachedto the carbon atoms directly bonded to the nitrogen atom; n is 1,2,3 or4; each Q is independently a monoanionic ligand, with the proviso thatwhere any Q is a hydrocarbyl radical, such Q is not a substituted orunsubstituted cyclopentadienyl radical; wherein R′ is a radical selectedfrom C₁-C₂₀ hydrocarbyl radical and substituted C₁-C₂₀ hydrocarbylradicals, wherein one or more hydrogen atoms is replaced by a halogenatom, amido, phosphido, alkoxy, aryloxy, metalloid, or a C₁-C₂₀hydrocarbyl-substituted metalloid radical wherein The metalloid isselected from Group 14 of the Periodic Table of the Elements; L_(w) is aneutral Lewis base; and w is a number from 0 to
 3. 6. A catalyst systemfor coordination polymerization comprising: (1) an activator, and (2) aGroup-3 or Lanthanide metal stabilized by a monoanionic bidentate ligandand two monoanionic ligands, wherein the bidentate ligand and the metalform a metallocyclic ring comprising at least five primary atoms, wherecomponent (2) is represented by the formula:

wherein M is scandium, yttrium or lanthanum; C₅H_(4-x)R_(x) is acyclopentadienyl ring covalently π-bound to M and substituted with fromzero to four substituent groups R; x is a number from 0 to 4 denotingthe degree of substitution of C₅H_(4-x)R_(x); each R is, independently,a radical selected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or other Lewisacidic or basic group, C₁-C₂₀ hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, and halogen radicals, or C₅H_(4-x)R_(x) is acyclopentadienyl ring in which two adjacent R-groups are joined to forma C₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand which may be additionally substituted with oneor more R groups; T is a covalent bridging group containing a Group 14or 15 element; J is a Group 15 or 16 element; z is 2 when J is a Group15 element and 1 when J is a Group 16 element; each R′ is independentlya radical selected from C₁-C₂₀ hydrocarbyl radicals, substituted C₁-C₂₀hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by ahalogen atom, and C₁-C₂₀ hydrocarbyl-substitute metalloid radicalwherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements; each Q is independently a univalent anionic ligand, andL_(w) is a neutral Lewis base; and w is a number from 0 to
 3. 7. Acatalyst system for coordination polymerization comprising: (1) anactivator, and (2) a Group-3 or Lanthanide metal stabilize by amonoanionic bidentate ligand and two monoanionic ligands, wherein thebidentate ligand and the metal form a metallocyclic ring comprising atleast five primary atoms, where component (2) is represented by theformula:

wherein M is a group 3 or Lanthanide metal; C₅H_(4-x)R_(x) is acyclopentadienyl ring covalently π-bound to M and substituted with fromzero to four substituent groups R; x is a number from 0 to 4 denotingthe degree of substitution of C₅H_(4-x)R_(x); each R is, independently,a radical selected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or other Lewisacidic or basic group, C₁-C₂₀ hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, and halogen radicals, or C₅H_(4-x)R_(x) is acyclopentadienyl ring in which two adjacent R-groups are joined to forma C₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand which may be additionally substituted with oneor more R groups; T is a dialkyl, alkylaryl, or diaryl silicon orgermanium radical; J is a Group 15 or 16 element; z is 2 when J is aGroup 15 element and 1 when J is a Group 16 element; each R′ isindependently a radical selected from C₁-C₂₀ hydrocarbyl radicals,substituted C₁-C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen atom, and C₂-C₂₀ hydrocarbyl-substitutemetalloid radical wherein the metalloid is selected from Group 14 of thePeriodic Table of the Elements; each Q is independently a univalentanionic ligand; and L_(w) is a neutral Lewis base; and w is a numberfrom 0 to
 3. 8. A catalyst system for coordination polymerizationcomprising: (1) an activator, and (2) a Group-3 or Lanthanide metalstabilize by a monoanionic bidentate ligand and two monoanionic ligands,wherein the bidentate ligand and the metal form a metallocyclic ringcomprising at least five primary atoms, where component (2) isrepresented by the formula:

wherein M is a group 3 or Lanthanide metal; C₅H_(4-x)R_(x) is acyclopentadienyl ring covalently π-bound to M and substituted with fromzero to four substituent groups R; x is a number from 0 to 4 denotingthe degree of substitution of C₅H_(4-x)R_(x); each R is, independently,a radical selected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or other Lewisacidic or basic group, C₁-C₂₀ hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, and halogen radicals, or C₅H_(4-x)R_(x) is acyclopentadienyl ring in which two adjacent R-groups are joined to forma C₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand which may be additionally substituted with oneor more R groups; T is an alkyl or aryl phosphine or amine radical or ahydrocarbyl radical; J is a Group 15 or 16 element; z is 2 when J is aGroup 15 element and 1 when J is a Group 16 element; each R′ isindependently a radical selected from C₁-C₂₀ hydrocarbyl radicals,substituted C₁-C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen atom, and C₂-C₂₀ hydrocarbyl-substitutemetalloid radical wherein the metalloid is selected from Group 14 of thePeriodic Table of the Elements; each Q is independently a univalentanionic ligand; and L_(w) is a neutral Lewis base; and w is a numberfrom 0 to
 3. 9. A catalyst system for coordination polymerizationcomprising: (1) an activator, and (2) a Group-3 or Lanthanide metalstabilized by a monoanionic bidentate ligand and two monoanionicligands, wherein the bidentate ligand and the metal form a metallocyclicring comprising at least five primary atoms, where component (2) isrepresented by the formula:

wherein M is a group 3 or Lanthanide metal; C₅H_(4-x)R_(x) is acyclopentadienyl ring covalently π-bound to M and substituted with fromzero to four substituent groups R; x is a number from 0 to 4 denotingthe degree of substitution of C₅H_(4-x)R_(x); each R is, independently,a radical selected from C₁-C₂₀ hydrocarbyl radicals, C₁-C₂₀ substitutedhydrocarbyl radicals wherein one or more hydrogen atoms are replaced bya halogen atom, amido, phosphido, alkoxy or aryloxy or other Lewisacidic or basic group, C₁-C₂₀ hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, and halogen radicals, or C₅H_(4-x)R_(x) is acyclopentadienyl ring in which two adjacent R-groups are joined to forma C₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand which may be additionally substituted with oneor more R groups; T is a covalent bridging group containing a Group 14or 15 element; J is oxygen, sulfur, nitrogen or phosphorous; z is 2 whenJ is a nitrogen or phosphorus and 1 when J is a oxygen or sulfur; eachR′ is independently a radical selected from C₁-C₂₀ hydrocarbyl radicals,substituted C₁-C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen atom, and C₂-C₂₀ hydrocarbyl-substitutemetalloid radical wherein the metalloid is selected from Group 14 of thePeriodic Table of the Elements; each Q is independently a univalentanionic ligand; and L_(w) is a neutral Lewis base; and w is a numberfrom 0 to
 3. 10. A catalyst system for coordination polymerizationcomprising: (1) an activator, and (2) a Group-3 or Lanthanide metalstabilize by a monoanionic bidentate ligand and two monoanionic ligands,wherein the bidentate ligand and the metal form a metallocyclic ringcomprising at least five primary atoms, where component (2) isrepresented by the formula:

wherein M is a group 3 or Lanthanide metal; L_(w) is a neutral Lewisbase; C₅H_(4-x)R_(x) is a cyclopentadienyl ring covalently π-bound to Mand substituted with from zero to four substituent groups R; x is anumber from 0 to 4 denoting the degree of substitution ofC₅H_(4-x)R_(x); each R is, independently, a radical selected from C₁-C₂₀hydrocarbyl radicals, C₁-C₂₀ substituted hydrocarbyl radicals whereinone or more hydrogen atoms are replaced by a halogen atom, amido,phosphido, alkoxy or aryloxy or other Lewis acidic or basic group,C₁-C₂₀ hydrocarbyl-substituted metalloid radicals wherein the metalloidis selected from Group 14 of the Periodic Table of the Elements, andhalogen radicals, or C₅H_(4-x)R_(x) is a cyclopentadienyl ring in whichtwo adjacent R-groups are joined to form a C₄-C₂₀ ring to give asaturated or unsaturated polycyclic cyclopentadienyl ligand which may beadditionally substituted with one or more R groups; T is a covalentbridging group containing a Group 14 or 15 element; J is nitrogen; z is2; each R′ is independently a radical selected from C₁-C₂₀ hydrocarbylradicals, substituted C₁-C₂₀ hydrocarbyl radicals wherein one or morehydrogen atoms is replaced by a halogen atom, and C₂-C₂₀hydrocarbyl-substitute metalloid radical wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements; each Q isindependently a univalent anionic ligand; and L_(w) is a neutral Lewisbase; and w is a number from 0 to
 3. 11. The catalyst system of claim 1where the activator comprises alumoxane.
 12. The catalyst system ofclaim 1 where the activator comprises methylalumoxane and/or modifiedmethylalumoxane.
 13. The catalyst system of claim 1 where the activatorcomprises modified alumoxane.
 14. The catalyst system of claim 1 wherethe activator comprises an alkylalumoxane, where the alkyl group isselected from the group consisting of methyl, ethyl, and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl and icosyl.
 15. The catalyst system of claim 1wherein the activator comprises a Lewis acid activator represented bythe formula ZX*₃R*_(b) wherein: R* is independently a C₁₋₃₀ hydrocarbyl,fluorohydrocarbyl, hydrocarbylsilyl or substituted hydrocarbyl group, Zis a group 13 element, X* is independently a substituted orunsubstituted fluorocarbyl or fluorohydrocarbyl ligand, and b is 0 or 1.16. The catalyst system of claim 1 wherein the activator comprises oneor more of B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃ orAl(C₁₂F₉)₃.
 17. The catalyst system of claim 1 wherein the catalystsystem is immobilized on a support.
 18. The catalyst system of claim 1wherein the catalyst system further comprises a scavenging compound. 19.The catalyst system of claim 1 wherein the catalyst system furthercomprises a scavenging compound selected from the group consisting oftriethyl aluminum, triethyl borane, triisobutyl aluminum,methylalumoxane, isobutyl aluminumoxane, triisoprenylaluminum,tri-n-hexylaluminum, tri-n-dodecylaluminum, and tri-n-octyl aluminum.20. The catalyst system of claim 1 wherein the catalyst system issupported on an inorganic oxide.
 21. The catalyst system of claim 1wherein the activator comprises an ionizing anion precursor compounds.22. The catalyst system of claim 1 wherein the activator comprises anoncoordinating anion precursor represented by the formula:[R*₂GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a Group 15 element, H is a proton, Z is a group13 element, X* is independently a substituted or unsubstitutedfluorocarbyl or fluorohydrocarbyl ligand, preferably a substituted orunsubstituted aromatic fluorocarbyl or fluorohydrocarbyl ligand, and ais 0, 1 or
 2. 23. The catalyst system of claim 1 wherein the activatorcomprises a cationic portion comprising one or more of [Me₂PhNH],[n-Bu₃NH], [(C₁₈H₃₇)₂PhNH], [(C₁₆H₃₃)₃NH], or [(C₁₈H₃₇)₃NH].
 24. Thecatalyst system of claim 1 wherein the activator comprises an anionicportion comprising one or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄],[MeB(C₆F₅)₃], [B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 25. Thecatalyst system of claim 1 wherein the activator comprises anoncoordinating anion precursor represented by the formula:[R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a nitrogen, H is a proton, Z is boron oraluminum, X* is independently a unsubstituted aromatic fluorocarbyl orfluorohydrocarbyl ligand, and a is 0, 1 or
 2. 26. The catalyst system ofclaim 2 where the activator comprises alumoxane.
 27. The catalyst systemof claim 2 where the activator comprises methylalumoxane and/or modifiedmethylalumoxane.
 28. The catalyst system of claim 2 where the activatorcomprises modified alumoxane.
 29. The catalyst system of claim 2 wherethe activator comprises an alkylalumoxane, where the alkyl group isselected from the group consisting of methyl, ethyl, and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl and icosyl.
 30. The catalyst system of claim 2wherein the activator comprises a Lewis acid activator represented bythe formula ZX*_(3-b)R*_(b) wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 31. The catalyst system of claim 2 wherein theactivator comprises one or more of B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃,Al(C₁₀F₇)₃, B(C₁₂F₉)₃ or Al(C₁₂F₉)₃.
 32. The catalyst system of claim 2wherein the catalyst system is immobilized on a support.
 33. Thecatalyst system of claim 2 wherein the catalyst system further comprisesa scavenging compound.
 34. The catalyst system of claim 2 wherein thecatalyst system further comprises a scavenging compound selected fromthe group consisting of triethyl aluminum, triethyl borane, triisobutylaluminum, methylalumoxane, isobutyl aluminumoxane, triisoprenylaluminum,tri-n-hexylaluminum, tri-n-dodecylaluminum, and tri-n-octyl aluminum.35. The catalyst system of claim 2 wherein the catalyst system issupported on an inorganic oxide.
 36. The catalyst system of claim 2wherein the activator comprises an ionizing anion precursor compound.37. The catalyst system of claim 2 wherein the activator comprises anoncoordinating anion precursor represented by the formula:[R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a Group 15 element, H is a proton, Z is a group13 element, X* is independently a substituted or unsubstitutedfluorocarbyl fluorohydrocarbyl ligand, preferably a substituted orunsubstituted aromatic fluorocarbyl or fluorohydrocarbyl ligand, and ais 0, 1 or
 2. 38. The catalyst system of claim 2 wherein the activatorcomprises a cationic portion comprising one or more of [Me₂PhNH],[n-Bu₃NH], [(C₁₈H₃₇)₂PhNH], [(C₁₆H₃₃)₃NH], or [(C₁₈H₃₇)₃NH].
 39. Thecatalyst system of claim 2 wherein the activator comprises an anionicportion comprising one or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄],[MeB(C₆F₅)₃], [B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 40. Thecatalyst system of claim 2 wherein the activator comprises anoncoordinating anion precursor represented by the formula:[R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a nitrogen, H is a proton, Z is boron oraluminum, X* is independently a unsubstituted aromatic fluorocarbyl orfluorohydrocarbyl ligand, and a is 0, 1 or
 2. 41. The catalyst system ofclaim 1 where M is scandium.
 42. The catalyst system of claim 41 wherethe activator comprises alumoxane.
 43. The catalyst system of claim 41where the activator comprises methylalumoxane and/or modifiedmethylalumoxane.
 44. The catalyst system of claim 41 where the activatorcomprises modified alumoxane.
 45. The catalyst system of claim 41 wherethe activator comprises an alkylalumoxane, where the alkyl group isselected from the group consisting of methyl, ethyl, and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl and icosyl.
 46. The catalyst system of claim 41wherein the activator comprises a Lewis acid activator represented bythe formula ZX*_(3-b)R*_(b) wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 47. The catalyst system of claim 41 wherein theactivator comprises one or more of B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃,Al(C₁₀F₇)₃, B(C₁₂F₉)₃, or Al(C₁₂F₉)₃.
 48. The catalyst system of claim41 wherein the catalyst system is immobilized on a support.
 49. Thecatalyst system of claim 41 wherein the catalyst system furthercomprises a scavenging compound.
 50. The catalyst system of claim 41wherein the catalyst system further comprises a scavenging compoundselected from the group consisting of triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, isobutyl aluminumoxane,triisoprenylaluminum, tri-n-hexylaluminum, tri-n-dodecylaluminum, andtri-n-octyl aluminum.
 51. The catalyst system of claim 41 wherein thecatalyst system is supported on an inorganic oxide.
 52. The catalystsystem of claim 41 wherein the activator comprises an ionizing anionprecursor compound.
 53. The catalyst system of claim 41 wherein theactivator comprises a noncoordinating anion precursor represented by theformula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a Group 15 element, H is a proton, Z is a group13 element, X* is independently a substituted or unsubstitutedfluorocarbyl fluorohydrocarbyl ligand, preferably a substituted orunsubstituted aromatic fluorocarbyl or fluorohydrocarbyl ligand, and ais 0, 1 or
 2. 54. The catalyst system of claim 41 wherein the activatorcomprises a cationic portion comprising one or more of [Me₂PhNH],[n-Bu₃NH], [(C₁₈H₃₇)₂PhNH], [(C₁₆H₃₃)₃NH], or [(C₁₈H₃₇)₃NH].
 55. Thecatalyst system of claim 41 wherein the activator comprises an anionicportion comprising one or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄],[MeB(C₆F₅)₃], [B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 56. Thecatalyst system of claim 41 wherein the activator comprises anoncoordinating anion precursor represented by the formula:[R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or other substitutedhydrocarbyl group, G is a nitrogen, H is a proton, Z is boron oraluminum, X* is independently a unsubstituted aromatic fluorocarbyl orfluorohydrocarbyl ligand, and a is 0, 1 or
 2. 57. The catalyst system ofclaim 3 wherein the activator comprises an alumoxane.
 58. The catalystsystem of claim 3 wherein the activator comprises a non-coordinatinganion.
 59. The catalyst system of claim 3 wherein the activatorcomprises a non-coordinating anion represented by the formula:[R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently a C₁₋₃₀hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylfluorohydrocarbyl ligand, and a is 0, 1 or
 2. 60. The catalyst system ofclaim 3 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 61. The catalyst system ofclaim 3 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 62. The catalyst system of claim 3 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.63. The catalyst system of claim 4 wherein the activator comprises analumoxane.
 64. The catalyst system of claim 4 wherein the activatorcomprises a non-coordinating anion.
 65. The catalyst system of claim 4wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 66. The catalyst systemof claim 4 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₂NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 67. The catalyst system ofclaim 4 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 68. The catalyst system of claim 4 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.69. The catalyst system of claim 5 wherein the activator comprises analumoxane.
 70. The catalyst system of claim 5 wherein the activatorcomprises a non-coordinating anion.
 71. The catalyst system of claim 5wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 72. The catalyst systemof claim 5 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 73. The catalyst system ofclaim 5 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 74. The catalyst system of claim 5 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₁, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.75. The catalyst system of claim 6 wherein the activator comprises analumoxane.
 76. The catalyst system of claim 6 wherein the activatorcomprises a non-coordinating anion.
 77. The catalyst system of claim 6wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylfluorohydrocarbyl ligand, and a is 0, 1 or
 2. 78. The catalyst system ofclaim 6 wherein the activator comprises; (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 79. The catalyst system ofclaim 6 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 80. The catalyst system of claim 6 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl baron.81. The catalyst system of claim 7 wherein the activator comprises analumoxane.
 82. The catalyst system of claim 7 wherein the activatorcomprises a non-coordinating anion.
 83. The catalyst system of claim 7wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 84. The catalyst systemof claim 7 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 85. The catalyst system ofclaim 7 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 86. The catalyst system of claim 7 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.87. The catalyst system of claim 8 wherein the activator comprises analumoxane.
 88. The catalyst system of claim 8 wherein the activatorcomprises a non-coordinating anion.
 89. The catalyst system of claim 8wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 90. The catalyst systemof claim 8 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 91. The catalyst system ofclaim 8 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 92. The catalyst system of claim 8 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.93. The catalyst system of claim 10 wherein the activator comprises analumoxane.
 94. The catalyst system of claim 10 wherein the activatorcomprises a non-coordinating anion.
 95. The catalyst system of claim 10wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 96. The catalyst systemof claim 10 wherein the activator comprises: (1) a cationic portioncomprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 97. The catalyst system ofclaim 10 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b) wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 98. The catalyst system of claim 10 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.99. The catalyst system of claim 9 wherein the activator comprises analumoxane.
 100. The catalyst system of claim 9 wherein the activatorcomprises a non-coordinating anion.
 101. The catalyst system of claim 9wherein the activator comprises a non-coordinating anion represented bythe formula: [R*₃GH][ZX*_(4-a)R*_(a)] wherein: R* is independently aC₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or a substitutedhydrocarbyl group, G is a Group 15 element, H is a proton capable ofreacting with the Group 3 or Lanthanide metal complex, Z is a group 13element, X* is independently a substituted or unsubstituted fluorocarbylor fluorohydrocarbyl ligand, and a is 0, 1 or
 2. 102. The catalystsystem of claim 9 wherein the activator comprises; (1) a cationicportion comprising one or more of [Me₂PhNH], [n-Bu₃NH], [(C₁₈H₃₇)₂PhNH],[(C₁₆H₃₃)₃NH] or [(C₁₈H₃₇)₃NH]; and or (2) an anionic portion comprisingone or more of [B(C₆F₅)₄], [B(C₁₀F₇)₄], [B(C₁₂F₉)₄], [MeB(C₆F₅)₃],[B(3,5-(CF₃)₂C₆H₃)₄], or [B(C₆F₅)₃(C₁₀F₇)].
 103. The catalyst system ofclaim 9 wherein the activator comprises an a Lewis acid activatorrepresented by the formula ZX*_(3-b)R*_(b), wherein: R* is independentlya C₁₋₃₀ hydrocarbyl, fluorohydrocarbyl, hydrocarbylsilyl or substitutedhydrocarbyl group, Z is a group 13 element, X* is independently asubstituted or unsubstituted fluorocarbyl or fluorohydrocarbyl ligand,and b is 0 or
 1. 104. The catalyst system of claim 9 wherein theactivator comprises one or more of methylalumoxane, modifiedmethylalumoxane, B(C₆F₅)₃, Al(C₆F₅)₃, B(C₁₀F₇)₃, Al(C₁₀F₇)₃, B(C₁₂F₉)₃,Al(C₁₂F₉)₃ and, N,N-Dimethylanilinium tetrakis-perfluorophenyl boron.